Polyamide 6/SiO2 hybrid materials were produced by a coupled polymerization reaction of three monomeric components namely 1,1',1'',1'''-silanetetrayltetrakis-(azepan-2-one) (Si(ε-CL)4), 6-aminocaproic acid (ε-ACA) and ε-caprolactam (ε-CL) within one process. Si(ε-CL)4 together with ε-ACA has been found suitable as precursor monomer for the silica and PA6 component. The accurate adjusting of the molar ratio of both components, as well as the combination of the overall process for producing the polyamide 6/SiO2 hybrid material with the hydrolytic ring opening polymerization of ε-caprolactam is of great importance to achieve homogeneous products with a low extractable content. Water in comparison to ε-ACA has been found unsuitable as oxygen source to produce uniformly distributed silica. The procedure was carried out in a commercial laboratory autoclave at 8 bar initial pressure. The molecular structure and morphology of the hybrid materials have been investigated by solid state 29 Si and 13 C NMR spectroscopy, DSC, FTIR spectroscopy and electron microscopic measurements.

Nanostructured aniline formaldehyde resin/polysilazane hybrid materials are produced by twin polymerization of 2,2′‐spirobi[3,4‐dihydro‐1H‐1,3,2‐benzodiazasiline] (1). An alternative synthetic concept for similar hybrid materials, the apparent twin polymerization, is employed by using the combination of the deficient twin monomer tetrakis(phenylamino)silane (2) with hexamethylenetetramine (HMTA). Both processes for the synthesis of polysilazane hybrid materials occur under volatilization of byproducts such as ammonia or aromatic nitrogen compounds. The thermal properties of the twin monomer 1 and the combination of 2/HMTA, respectively, are investigated by differential scanning calorimetry and thermogravimetric analysis. Aniline‐formaldehyde resin/polysilazane hybrid materials are characterized by solid state 13C‐ and 29Si‐NMR spectroscopy and transmission electron microscopy. The inorganic network remains hydrolyzable and can be functionalized after polymerization at temperatures below 500 °C due to residuary reactive Si−N bonds. Thermal treatment at 1100 °C leads to the formation of amorphous Si/C/N hybrid materials.

The addition polymerization of aromatic disecondary diamines and 2,2-bis[4-(2,3-epoxypropoxy)phenyl]propane (DGEBA) leads to linear high molecular weight epoxideamine addition polymers with number-average molecular weights ranging from 10000 to 20000 g/mol. Depending on the amine structure, their glass transition temperatures were estimated between 80 and 140°C. The fractionation of the high molecular weight addition polymers allows the separation of cyclic --oligomers and the separation of polymers with narrow molecular weight distribution (MJM,, = 2.4-2.8). In dilute solution, predominantly cyclic oligomers were formed. Hence, they were prepared in such solutions and isolated by means of column chromatography. Their cyclic structure is proved by combination of a values and I3C NMR spectra.

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